تفاعل #86459

معادلة التفاعل

2-chloro-6-fluoro-3,5-dimethoxybenzoic acid

triethyl amine

TFA

Diphenyl phosphoryl azide

→

title compound

المردود 60.0%

2-chloro-6-fluoro-3,5-dimethoxyaniline

المردود 60.0%

المذيبات

tert-BuOH

dichloromethane

ظروف التفاعل

المعالجة

1. 1
   workup.ADDITIONwas added
2. 2
   workup.WAITkept at this temperature for overnight
3. 3
   تركيزThe reaction mixture was then concentrated in vacuo
4. 4
   أخرىto obtain a crude residue
5. 5
   درجة الحرارةcooled to 0° C
6. 6
   أخرىthe resultant reaction mixture
7. 7
   workup.STIRRINGwas then stirred at room temperature for 2 h
8. 8
   أخرىThe solvents were removed under vacuum
9. 9
   workup.ADDITIONthe crude residue was diluted with ethyl acetate and saturated sodium carbonate solution
10. 10
    أخرىThe aqueous layer was separated
11. 11
    استخلاصextracted with ethyl acetate (3×30 mL)
12. 12
    غسيلThe organic phase was washed with brine
13. 13
    تجفيفdried over Na2SO4
14. 14
    ترشيحfiltered
15. 15
    تركيزconcentrated
16. 16
    أخرىThe residue was purified by silica gel column chromatography

الإجراء التجريبي

A suspension of 2-chloro-6-fluoro-3,5-dimethoxybenzoic acid (10.8 g, 0.0077 mol) and triethyl amine (0.934 g, 0.0092 mol) in tert-BuOH (50 mL) was stirred for 5 min. To the resulting reaction mixture, Diphenyl phosphoryl azide (2.53 g, 0.0092 mol) was added and heated up to 82° C. and kept at this temperature for overnight. The reaction mixture was then concentrated in vacuo to obtain a crude residue. The crude residue was dissolved in dichloromethane (20 mL) and cooled to 0° C. TFA (4 mL) was added to the reaction mixture and the resultant reaction mixture was then stirred at room temperature for 2 h. The solvents were removed under vacuum and the crude residue was diluted with ethyl acetate and saturated sodium carbonate solution. The aqueous layer was separated and extracted with ethyl acetate (3×30 mL). The organic phase was washed with brine, dried over Na2SO4, filtered, and concentrated. The residue was purified by silica gel column chromatography using the eluent (gradient hexane to hexane-ether (65:35)) to afford the title compound (0.95 g, yield: 60%) as solid. MS (ESI): 205.7 [M+H]+.

المصدر